EP0174132A2 - Bleichaktivatorzusammensetzungen, deren Herstellung und Verwendung in Wäschewaschmitteln - Google Patents

Bleichaktivatorzusammensetzungen, deren Herstellung und Verwendung in Wäschewaschmitteln Download PDF

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EP0174132A2
EP0174132A2 EP85305933A EP85305933A EP0174132A2 EP 0174132 A2 EP0174132 A2 EP 0174132A2 EP 85305933 A EP85305933 A EP 85305933A EP 85305933 A EP85305933 A EP 85305933A EP 0174132 A2 EP0174132 A2 EP 0174132A2
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Prior art keywords
water
composition
bleach
range
composition according
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French (fr)
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EP0174132A3 (en
EP0174132B1 (de
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Michael Divo
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
Procter and Gamble Co
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3935Bleach activators or bleach catalysts granulated, coated or protected
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to bleach activator compositions. More particularly, it relates to bleach activator compositions prepared by spray drying for use in or with a detergent and/or bleach composition.
  • the bleach activator compositions have excellent storage stability, physical strength and water-dispersibility, as well as simplified processing and reduced segregation in a full detergent or bleach product.
  • the invention also relates to a process of making the compositions and also to laundry compositions containing water-soluble bleach activators.
  • peroxygen bleaching agents e.g., perborates, percarbonates, perphosphates, persilicates etc.
  • bleaching agents are highly useful for chemical bleaching of stains found on both colored and white fabrics.
  • Such bleaching agents are most effective at high wash solution temperatures, i.e., above about 60°C to 70°C.
  • bleach activators that render peroxygen bleaches effective at bleach solution temperatures below 60°C.
  • These low temperature bleaches are useful in a variety of products intended for use under machine or hand-wash conditions, e.g., additive pre-additive or soak-type laundry compositions as well as all-purpose detergent compositions.
  • a bleach activator can generally be described as an organic peroxy acid bleach precursor which in the bleaching solution reacts with an inorganic peroxygen bleaching agent with release of the organic peroxy acid.
  • bleach activators are known in the art, most of which contain perhydrolysable N-acyl or 0-acyl residues. Examples of these include succinic, benzoic and phthalic anhydrides, tetracetylethylene diamine and tetracetylglycouril, all of which are water-insoluble materials to varying degrees.
  • Water-soluble bleach activators are also known in the act and are described in detail in, for example, US-A-4,412,934 and European Patent Application No. 84301070.3. These activators have a number of advantages over water-insoluble materials including rapid dispersibility in wash or bleach solution and also the ability to exhibit surface bleaching. On the downside, however, water-solubility greatly exacerbates activator stability problems resulting from interaction with moisture and peroxygen bleaching agent during prolonged storage in the bleach or detergent composition.
  • water-soluble bleach activators can be successfully crutched and spray-dried by incorporating an inorganic hydratable material in the crutcher slurry mix and adjusting the pH of the slurry to within the range from about 3 to about 8 prior to spray-drying.
  • the subsequent granule is found to combine excellent stability characteristics when stored in a detergent or bleach composition, as well as improved dispersibility on addition to the wash or bleach solution.
  • a bleach activator composition in the form of spray-dried granules having an inner core comprising water-soluble organic peroxyacid bleach precursor and a surface coating comprising a water-soluble or water-dispersible, inorganic hydratable material, and wherein the composition has a pH (1% aqueous solution) in the range from about 3 to about 8.
  • the invention also relates to a process of making a granular bleach activator composition
  • a process of making a granular bleach activator composition comprising forming an aqueous slurry of a water-soluble organic peroxyacid bleach precursor and a water-soluble or water-dispersable inorganic hydratable material, adjusting the pH of the slurry (1% solids) to within the range from about 3 to about 8, preferably from about 3.5 to about 7 and subjecting the slurry to spray-drying.
  • compositions of the invention generally take the form of granules having an inner core comprising water-soluble bleach precursor encapsulated or substantially enclosed within a coating of water-soluble or dispersible inorganic hydratable material.
  • the inner core exists as an essentially spherical drcplet or aggregation of spherical droplets of the bleach precursor.
  • the outer coating on the other hand comprises a water-soluble or water-dispersible inorganic hydratable material which in preferred embodiments, consists majorly (at least about 50%, preferably at least about 75%) of one or more acid salts having a pK a in the range from about 1 to about 9, preferably from about 2 to about 7, more preferably from about 3 to about 6.5.
  • Suitable inorganic hydratable materials include disodium dihydrogen pyrophosphate, tetrasodium monohydrogen tripolyphosphate, trisodium dihydrogen tripolyphosphate, sodium bicarbonate, acidified pentasodium tripolyphosphate, acidified borax and acidified aluminosilicates and mixtures thereof.
  • the hydratable material is preferably hydrated to an extent of from about 10% to about 90%, preferably from about 30% to about 60% of its hydration capacity (based on the highest hydrate which is stable at room temperature).
  • the inorganic hydratable material has no hydrate transition point below about 40 0 C or consists majorly of such material (greater than about 50%, preferably greater than about 75% of total inorganic hydratable material).
  • pH control is all-important both for successful spray drying of the aqueous slurry mix and for stability of the resulting granular composition.
  • the provision of a pH-regulated outer coating based on partly-hydrated inorganic hydratable material appears to be especially beneficial in providing both physical and chemical stabilization of the water-soluble bleach activator in the final detergent or bleach product.
  • the pH of the granular composition (1% aqueous solution) should lie within the range from about 3 to about 8, preferably from about 3.5 to about 7, more preferably from about 4 to about 6.5, while the aqueous slurry for spray-drying should also be adjusted to within the same pH range (1% solids solution).
  • Adjustment of pH can be achieved in various ways, for example, by incorporating inorganic acid salts having the required pH characteristics, or by adding mineral acids or organic acids to the crutcher mix to lower the pH into the prescribed range.
  • Suitable organic acids herein include C 8 -C 24 fatty acids, polycarboxylic acids, aminopolycarboxylic acids, polyphosphonic acids, aminopolyphosphonic acids and mixtures thereof.
  • the spray-dried granular bleach activator compositions herein generally comprise from about 0.1% to about 50%, preferably from about 1% to about 45% bleach precursor, and from about 10% to about 99.9%, preferably from about 25% to about 90% alkaline inorganic hydratable material.
  • they generally have a bulk density of from about 300 to about 900 grams/litre, preferably from about 450 to about 750 grams/litre, and a weight average particle size of from about 0.15 to about 3mm, preferably from about 0.5nm to about 1.4mm.
  • the aqueous slurry for spray drying comprises generally from about 30% to about 60% water, from about 0.05% to about 35%, preferably from about 0.5% to about 30%, more preferably from about 2% to about 25% bleach precursor, and from about 10% to about 69.95%, preferably from about 14% to about 63% alkaline inorganic hydratable material.
  • the slurry is then heated to a temperature of from about 60°C to about 90°C and spray-dried in a current of air having an inlet temperature of from about 250°C to about 350°C, preferably from about 275°C to about 330°C, and an outlet temperature of from about 95°C to about 125°C, preferably from about 100°C to about 115°C.
  • the bleach activators used in the compositions and process of the invention are water-soluble materials, being soluble generally to an extent of at least about 1%, preferably at least about 5% by weight at 25°C and pH 7.
  • 'soluble' is meant that the bleach activator/water system is free of solids at the specified concentration.
  • the preferred bleach activator herein is a peroxyacid bleach precursor haing the general formula I wherein R is an optionally substituted alkyl group containing from 6 to 12 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 5 to 10 carbon atoms and L is a leaving group containing an anionic moiety, the conjugate acid of the leaving group having a pK a in the range from 6 to 13.
  • the group R can be either linear or branched and, in preferred embodiments, it is unsubstituted and contains from 7 to 9 carbon atoms.
  • the group R is substituted and has the general formula II wherein R 1 is straight or branched chain alkyl containing from 4 to 10, preferably 6 to 10, more preferably 6 to 8 carbon atans, R 2 is H, CH 3 , C 2 H 5 or C 3 H 7 and X is Cl, Br, OCH 3 or OC 2 H 5 .
  • L can be essentially any suitable leaving group containing a moiety which is anionic at pH 7.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion.
  • Leaving groups that exhibit such behavior are those in which their conjugate acid has a pK a in the range of from 6 to 13, preferably from 7 to 11 and most preferably from about 8 to about 11.
  • suitable anionic moieties are -SO 3 M, -COOM and -OS0 3 M wherein M is a proton or a compatible cation.
  • Preferred bleach activators are those of the general formula I wherein L is selected from and wherein Z is H, R 3 or halogen, R 3 is an alkyl group having from 1 to 4 carbon atoms, x is 0 or an integer of from 1 to 4 and Y is selected from SO 3 M, OSO 3 M and CO 2 M and wherein M is H, alkali metal, alkaline earth metal, amnonium or substituted ammonium.
  • the preferred leaving group L has the formula (a) in which Z is H, x is 0 and Y is sulfonate or carboxylate.
  • Highly preferred materials are sodium 3,5,5,-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5, trimethexanoyloxybenzoate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate, sodium octanoyl oxybenzenesulfonate,sodium 2-chlorooctanoyloxybenzenesulfonate, sodium 2-chlorononanoyloxybenzenesulfonate, sodium 3,5,5-trimethyl-2-chlorohexanoyloxybenzene sulfonate, and sodium 2-chloro-2-ethyl-hexanoyloxybenzenesulfonate, the acyloxy group in
  • the present invention also encompasses bleaching compositions, laundry detergent and laundry additive compositions comprising the bleach activator compositions detailed herein as well as laundry compositions incorporating the water-soluble bleach activator and detergent in a co-dried granule.
  • Bleaching compositions according to the invention suitably contain from about 5% to about 99.5%, preferably from about 20% to about 90% of peroxygen bleaching agent and from about 0.5% to about 95%, preferably from about 10% to about 80% of bleach activator composition.
  • Laundry compositions according to the invention generally contain from about 2% to about 40%, preferably from about 5% to about 25% of detersive surfactant selected from anionic, nonionic, cationic, ampholytic and zwitterionic surfactants and mixtures thereof and from about 0.1% to about 20%, preferably from about 0.5% to about 10% of the water-soluble organic peroxyacid bleach precursor.
  • the surfactant and bleach precursor can either be co-spray dried or the surfactant can be incorporated in a separate laundry base composition.
  • the spray dried granules contain the water-soluble or water-dispersible inorganic hydratable material at a level of from about 10% to about 90%, preferably from about 15% to about 70% by weight of the laundry composition and the spray-dried granules generally constitute from about 15% to 100%, preferably from about 25% to about 75% by weight of the laundry composition.
  • the surfactant is incorporated in a separate laundry base component
  • the bleach activator composition generally comprises from about 0.5% to about 40%, preferably from 1% to about 10% by weight of the laundry composition
  • the base composition comprises from about 25% to about 99.5%, preferably from 35% to about 75% by weight of the laundry composition.
  • the laundry compositions generally comprise one or more inorganic or organic detergency builders in a total level of from about 15% to about 90%, preferably from about 20% to about 60% by weight of the laundry composition, and peroxygen bleaching agent in a level of from about 5% to about 35%, preferably from about 8% to about 20% by weight of the laundry composition.
  • a wide range of surfactants can be used in the laundry compositions of the invention.
  • US-A-4,111,855 and US-A-3,995,669 contain detailed listing of typical detersive surfactants.
  • Suitable synthetic anionic surfactants are water-soluble salts of C 8 -C 22 alkyl benzene sulphonates, C 8 -C 22 alkyl sulphates, C 10-18 alkyl polyethoxy ether sulphates, C 8-24 paraffin sulphonates, alpha- C 12-24 olefin sulphonates, alpha-sulphonated C 6 -C 20 fatty acids and their esters, C 10 -C 18 alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, especially those prepared from coconut oil, C 8 -C 12 alkyl phenol polyethoxy ether sulphates, 2-acyloxy C 9 -C 23 alkane-1-sulphonate, and beta-alkyloxy C 8 -C 20 alkane sulphonates.
  • a particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester group.
  • alkyl is the alkyl portion of acyl groups).
  • this group of synthetic detergents are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C 8-18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • alkane chains of the foregoing non-soap anionic surfactants can be derived fran natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred.
  • Suitable fatty acid soaps herein can be selected from the ordinary alkali metal (sodium, potassium), ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24, preferably from about 10 to about 22 and especially from about 16 to about 22 carbon atoms in the alkyl chain.
  • Fatty acids in partially neutralized form are also suitable for use herein, especially in liquid compositions.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.
  • Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from about 5:1 to about 1:5, preferably from about 5:1 to about 1:1, more preferably from about 5:1 to about 1.5:1.
  • an alkyl benzene sulphonate having from 9 to 15, especially 11 to 13 carbon atans in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an alkyl sulphate having from 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical or an ethoxy sulphate having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.
  • nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from about 8 to 17, preferably from about 9.5 to 13.5, more preferably from about 10 to about 12.5.
  • HLB hydrophilic-lipophilic balance
  • nonionic surfactants include the condensation products of primary or secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 2 to about 40 moles, preferably 2 to about 9 moles of ethylene oxide per mole of alcohol.
  • the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol.
  • the preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g.
  • myristyl, cetyl, stearyl alcohols or partly branched such as the Lutensols, Dobanols and Neodols which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol and Neodol being Trade Names of Shell), or Synperonics, which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica.
  • Lutensol being a Trade Name of BASF
  • Dobanol and Neodol being Trade Names of Shell
  • Synperonics which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica.
  • nonionic surfactants falling within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atans.
  • Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol series having from about 9 to 15 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.
  • nonionic surfactants include the condensation products of C 6 -C 12 alkyl phenols with from about 3 to 30, preferably 5 to 14 moles of ethylene oxide, and the compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with prcpylene glycol, such synthetic nonionic detergents being available on the market under the Trade Name of "Pluronic" supplied by Wyandotte Chemicals Corporation.
  • Especially preferred nonionic surfactants for use herein are the C 9 -C 15 primary alcohol ethoxylates containirg 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 12 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.
  • Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surfactants of a semi-polar nature, for example amine oxides.
  • Suitable quaternary ammonium surfactants are selected from mono C 8 -C 16 , preferably C 10 -C 14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl and the corresponding di-C 6 -C 10 N-alkyl or alkenyl ammonium surfactants.
  • Suitable amine oxides are selected from mono C 8 -C 20 , preferably C 10 -C 14 N-alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides wherein the remaining N positions are again substituted by methyl, hydroxyethyl or hydroxyprcpyl.
  • Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, pyrophosphates, tripolyphosphates and bicarbonates.
  • Organic builder/chelating agents that can be incorporated include citric acid, nitrilotriacetic and ethylenediamine tetra acetic acids and their salts, organic phosphonate derivatives such as those disclosed in US-A-3,213,030, US-A-3,433,021, US-A-3,292,121 and US-A-2,599,807, and carboxylic acid builder salts such as those disclosed in US-A-3,308,067.
  • Preferred chelating agents include nitrilotriacetic acid (NTA), nitrilo(trimethylene phosphonic acid) (NTMP), ethylenediamine tetra(methylene phosphonic acid) (EDTMP) and diethylenetriamine penta(methylene phosphonic acid) (DETPMP).
  • NTA nitrilotriacetic acid
  • NTMP nitrilo(trimethylene phosphonic acid)
  • ETMP ethylenediamine tetra(methylene phosphonic acid)
  • DETPMP diethylenetriamine penta(methylene phosphonic acid)
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in CA-A-755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • a further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution.
  • a preferred builder of this type has the formulation Na z (AlO 2 ) z (SiO 2 ) y .xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 264.
  • Compositions incorporating builder salts of this type form the subject of GB-A-1,429,143, DE-A-2,433,485, and DE-A-2,525,778.
  • alkali metal, or alkaline earth metal, silicate can also be present in granular compositions of the invention.
  • the alkali metal silicate is preferably from about 3% to about 15%.
  • Suitable silicate solids have a molar ratio of SiO 2/ alkali metal 2 O in the range from about 1.0 to about 3.3, more preferably from 1.5 to 2.0.
  • compositions herein can also contain bleaching components.
  • the bleach is selected from inorganic peroxy salts, hydrogen peroxide, hydrogen peroxide adducts, and organic peroxy acids and salts thereof.
  • Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahydrate, sodium percarbonate, sodium persilicate, urea-hydrogen peroxide addition products and the clathrate 4Na 2 SO 4 :2H 2 O 2 :1NaCl.
  • Suitable organic bleaches include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono- and diperoxyiscphthalic acid.
  • compositions of the invention can be supplemented by all manner of detergent and laundering components, inclusive of suds suppressors, enzymes, fluorescers, photoactivators, soil suspending agents, anti-caking agents, pigments, perfumes, fabric conditioning agents etc.
  • Suds suppressors are represented by materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties.
  • Suitable silicone suds controlling agents include polydimethylsiloxanes having a molecular weight in the range from about 200 to about 200,000 and a kinematic viscosity in the range from about 20 to about 2,000,000 mm 2 /s, preferably from about 3000 to about 30,000 mm 2 /s, and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to about 20 millimicrons and a specific surface area above about 50 m 2 /g.
  • Suitable waxes include microcrystalline waxes having a melting point in the range from about 65 0 C to about 100°C, a molecular weight in the range from about 4000-1000, and a penetration value of at least 6, measured at 770C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes.
  • Suitable phosphate esters include mono- and/o r di- C 16 -C 22 alkyl or alkenyl phosphate esters, and the corresponding mono- and/or di alkyl or alkenyl ether phosphates containing up to 6 ethoxy groups per molecule.
  • Enzymes suitable for use herein include those discussed in US-A-3,519,570 and US-A-3,533,139.
  • Suitable fluorescers include Blankcphor MBBH (Bayer AG) and Tinopal CBS and EMS (Ciba Geigy).
  • Photoactivators are discussed in EP-A-57088, highly preferred materials being zinc phthalocyanine, tri- and tetra-sulfonates.
  • Suitable fabric conditioning agents include smectite-type clays as disclosed in GB-A-1400898 and di-C 12 -C 24 alkyl or alkenyl amines and ammonium salts.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric-polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1,596,756.
  • Preferred polymers include copolymers or salts thereof of maleic anhydride with ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic anhydride constituting at least about 20 mole percent of the copolymer. These polymers are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Laundry additive products comprising bleaching or laundry detergent compositions in water-releasable combination with a non-particulate carrier as described in EP-A-96566 and EP-A-99197, are also suitable herein.
  • a preferred carrier takes the form of a flexible sheet-like substrate, for example, an apertured non-woven fabric made of rayon with a nonionic self-crosslinking acrylic polymer as binder, the weight ratio of bleaching or bleaching detergent composition to substrate being at least about 1:1, preferably at least about 3:1, more preferably at least about 6:1.
  • Carriers in the form of laminates, pouches and the like are also suitable, however.
  • Granular detergent compositions are prepared as follows.
  • a detergent base powder composition is first prepared by mixing the indicated components in a crutcher as an aqueous slurry at a temperature of about 700C and containing about 35% water. The slurry is then spray dried at a gas inlet temperature of about 300 0 C to form base powder granules.
  • the detergent base powder contains water-soluble bleach activator in addition to the detersive components.
  • a separate bleach activator composition is prepared by mixing the indicated components in a crutcher at a temperature of about 70°C and containing about 38% water, the slurry being spray dried at a gas inlet temperature of about 300°C and a gas outlet temperature of about 100°C.
  • the detergent base powder composition is dry mixed with enzyme, silicate, carbonate, bleach and spray-dried bleach activator components, where present, and additional nonionic surfactant acid, where present, is sprayed onto the total mixture.
  • the above products combine excellent bleach activator stability, water-dispersibility, granulometry and detergency performance across the range of wash temperatures and soil types.

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EP85305933A 1984-09-01 1985-08-21 Bleichaktivatorzusammensetzungen, deren Herstellung und Verwendung in Wäschewaschmitteln Expired EP0174132B1 (de)

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AT85305933T ATE39266T1 (de) 1984-09-01 1985-08-21 Bleichaktivatorzusammensetzungen, deren herstellung und verwendung in waeschewaschmitteln.

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GB8422158 1984-09-01
GB848422158A GB8422158D0 (en) 1984-09-01 1984-09-01 Bleach compositions

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EP0174132A2 true EP0174132A2 (de) 1986-03-12
EP0174132A3 EP0174132A3 (en) 1986-06-11
EP0174132B1 EP0174132B1 (de) 1988-12-14

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US4906399A (en) * 1988-08-19 1990-03-06 Dow Corning Corporation Organosilicon oxygen bleach activator compositions
EP0402971A2 (de) * 1989-06-14 1990-12-19 Unilever N.V. Partikelförmiges Waschmittelzusammensetzungsadditiv
EP0482807A1 (de) * 1990-10-23 1992-04-29 WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) Wieder freisetzbar eingekapselte, aktive Substrate
US5114606A (en) * 1990-02-19 1992-05-19 Lever Brothers Company, Division Of Conopco, Inc. Bleaching composition comprising as a bleaching catalyst a complex of manganese with a non-carboxylate polyhydroxy ligand
US5259981A (en) * 1992-01-17 1993-11-09 Lever Brothers Company Detergent compositions
US5259982A (en) * 1992-01-17 1993-11-09 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
EP0783035A2 (de) 1996-01-04 1997-07-09 Hoechst Aktiengesellschaft Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze
EP0791647A2 (de) 1996-02-21 1997-08-27 Hoechst Aktiengesellschaft Bleichmittel
WO1998000515A1 (en) * 1996-06-28 1998-01-08 The Procter & Gamble Company Coated particle-containing, non-aqueous liquid cleaning compositions
US5850086A (en) * 1996-06-21 1998-12-15 Regents Of The University Of Minnesota Iron complexes for bleach activation and stereospecific oxidation
WO2000077160A1 (fr) * 1999-06-16 2000-12-21 Kao Corporation Detergent particulaire
US6537959B2 (en) 2000-05-12 2003-03-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleach catalyst and composition and method for bleaching a substrate
US6551977B2 (en) 2001-03-14 2003-04-22 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Air bleaching catalysts with enhancer and moderating agent
US6586383B2 (en) 2001-03-14 2003-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Air bleaching catalysts with moderating agent
WO2012000846A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
WO2012080088A1 (en) 2010-12-13 2012-06-21 Basf Se Bleach catalysts
US8551979B2 (en) * 2004-11-05 2013-10-08 Lead Chemical Co., Ltd. Nonaqueous preparation for percutaneous absorption containing nonsteroidal anti-inflammatory analgesic
WO2014202954A1 (en) 2013-06-20 2014-12-24 Chemsenti Limited Bleach and oxidation catalyst
WO2017076771A1 (en) 2015-11-03 2017-05-11 Basf Se Bleach catalysts
EP3176157A1 (de) 2015-12-01 2017-06-07 Basf Se Bleichkatalysatoren
WO2017182295A1 (en) 2016-04-18 2017-10-26 Basf Se Liquid cleaning compositions
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition
EP3372663A1 (de) 2017-03-10 2018-09-12 Basf Se Bleichkatalysatoren
US10370621B2 (en) 2013-08-16 2019-08-06 Chemsenti Limited Bleaching formulations comprising particles and transition metal ion-containing bleaching catalysts
EP3524347A1 (de) 2008-04-09 2019-08-14 Basf Se Verwendung von metallhydrazidkomplexverbindungen als oxidationskatalysatoren
WO2021170840A1 (en) 2020-02-28 2021-09-02 Catexel Technologies Limited Degradative method
EP3967742A1 (de) 2020-09-15 2022-03-16 WeylChem Performance Products GmbH Bleichkatalysatorhaltige zusammensetzungen, verfahren zu ihrer herstellung und bleich- und reinigungsmittel damit
EP4008765A1 (de) 2020-12-07 2022-06-08 WeylChem Performance Products GmbH Zusammensetzungen mit protonierten triazacyclischen verbindungen und bleichmittel und reinigungsmittel damit
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JP2551991B2 (ja) * 1989-01-25 1996-11-06 花王株式会社 カビ取り剤組成物
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EP1239025A3 (de) 2001-03-03 2003-09-03 Clariant GmbH Waschmittel und Wäschebehandlungsmittel enthaltend farbübertragungsinhibierend Farbfixiermittel
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JP4532779B2 (ja) * 2001-05-21 2010-08-25 花王株式会社 漂白活性化剤造粒物及び漂白剤組成物
DE10361081A1 (de) * 2003-06-13 2005-01-05 Henkel Kgaa Verfahren zur Stabilisierung von Peroxycarbonsäuren in tensidhaltigen Dispersionen
DE102004018051A1 (de) * 2004-04-08 2005-11-10 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend Farbfixiermittel und Soil Release Polymere
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NO20073834L (no) * 2006-07-21 2008-01-22 Akzo Nobel Chemicals Int Bv Sulfonerte podede kopolymerer
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JPWO2011118340A1 (ja) * 2010-03-26 2013-07-04 ライオン株式会社 漂白活性化剤造粒物及びその製造方法
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
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JP2014532791A (ja) 2011-11-04 2014-12-08 アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップAkzo Nobel Chemicals International B.V. ハイブリッド樹状コポリマー、その組成物及びそれを製造する方法
EP2773321B1 (de) 2011-11-04 2015-09-09 Akzo Nobel Chemicals International B.V. Dendrit-pfropfcopolymere und verfahren zu ihrer herstellung
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0236270A2 (de) * 1986-02-28 1987-09-09 Ciba-Geigy Ag Verfahren zur Herstellung von eine Wirksubstanz enthaltenden Körpern und deren Verwendung als Speckles
EP0236270A3 (de) * 1986-02-28 1989-06-28 Ciba-Geigy Ag Verfahren zur Herstellung von eine Wirksubstanz enthaltenden Körpern und deren Verwendung als Speckles
US4906399A (en) * 1988-08-19 1990-03-06 Dow Corning Corporation Organosilicon oxygen bleach activator compositions
EP0402971A2 (de) * 1989-06-14 1990-12-19 Unilever N.V. Partikelförmiges Waschmittelzusammensetzungsadditiv
EP0402971A3 (de) * 1989-06-14 1991-03-27 Unilever N.V. Partikelförmiges Waschmittelzusammensetzungsadditiv
US5114606A (en) * 1990-02-19 1992-05-19 Lever Brothers Company, Division Of Conopco, Inc. Bleaching composition comprising as a bleaching catalyst a complex of manganese with a non-carboxylate polyhydroxy ligand
EP0482807A1 (de) * 1990-10-23 1992-04-29 WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) Wieder freisetzbar eingekapselte, aktive Substrate
US5259981A (en) * 1992-01-17 1993-11-09 Lever Brothers Company Detergent compositions
US5259982A (en) * 1992-01-17 1993-11-09 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
EP0783035A2 (de) 1996-01-04 1997-07-09 Hoechst Aktiengesellschaft Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze
EP0791647A2 (de) 1996-02-21 1997-08-27 Hoechst Aktiengesellschaft Bleichmittel
US5850086A (en) * 1996-06-21 1998-12-15 Regents Of The University Of Minnesota Iron complexes for bleach activation and stereospecific oxidation
US6107528A (en) * 1996-06-21 2000-08-22 Regents Of The University Of Minnesota Iron complexes for bleach activation and stereospecific oxidation
WO1998000515A1 (en) * 1996-06-28 1998-01-08 The Procter & Gamble Company Coated particle-containing, non-aqueous liquid cleaning compositions
WO2000077160A1 (fr) * 1999-06-16 2000-12-21 Kao Corporation Detergent particulaire
US6537959B2 (en) 2000-05-12 2003-03-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleach catalyst and composition and method for bleaching a substrate
US6551977B2 (en) 2001-03-14 2003-04-22 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Air bleaching catalysts with enhancer and moderating agent
US6586383B2 (en) 2001-03-14 2003-07-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Air bleaching catalysts with moderating agent
US8551979B2 (en) * 2004-11-05 2013-10-08 Lead Chemical Co., Ltd. Nonaqueous preparation for percutaneous absorption containing nonsteroidal anti-inflammatory analgesic
EP3524347A1 (de) 2008-04-09 2019-08-14 Basf Se Verwendung von metallhydrazidkomplexverbindungen als oxidationskatalysatoren
WO2012000846A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
EP2805942A1 (de) 2010-12-13 2014-11-26 Basf Se Bleichkatalysatoren
WO2012080088A1 (en) 2010-12-13 2012-06-21 Basf Se Bleach catalysts
WO2014202954A1 (en) 2013-06-20 2014-12-24 Chemsenti Limited Bleach and oxidation catalyst
US10370621B2 (en) 2013-08-16 2019-08-06 Chemsenti Limited Bleaching formulations comprising particles and transition metal ion-containing bleaching catalysts
WO2017076771A1 (en) 2015-11-03 2017-05-11 Basf Se Bleach catalysts
EP3176157A1 (de) 2015-12-01 2017-06-07 Basf Se Bleichkatalysatoren
WO2017182295A1 (en) 2016-04-18 2017-10-26 Basf Se Liquid cleaning compositions
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition
EP3372663A1 (de) 2017-03-10 2018-09-12 Basf Se Bleichkatalysatoren
WO2021170840A1 (en) 2020-02-28 2021-09-02 Catexel Technologies Limited Degradative method
EP3967742A1 (de) 2020-09-15 2022-03-16 WeylChem Performance Products GmbH Bleichkatalysatorhaltige zusammensetzungen, verfahren zu ihrer herstellung und bleich- und reinigungsmittel damit
WO2022058039A1 (en) 2020-09-15 2022-03-24 WeylChem Performance Products GmbH Compositions comprising bleaching catalyst, manufacturing process thereof, and bleaching and cleaning agent comprising same
EP4008765A1 (de) 2020-12-07 2022-06-08 WeylChem Performance Products GmbH Zusammensetzungen mit protonierten triazacyclischen verbindungen und bleichmittel und reinigungsmittel damit
WO2022122177A1 (en) 2020-12-07 2022-06-16 WeylChem Performance Products GmbH Granules comprising protonated triazacyclic compounds and bleaching agent and cleaning agent comprising the same
EP4296344A1 (de) 2022-06-24 2023-12-27 WeylChem Performance Products GmbH Zusammensetzungen mit protonierten triazacyclischen verbindungen und mangan(ii)-acetat, herstellung davon und bleich- und reinigungsmittel damit
EP4296343A1 (de) 2022-06-24 2023-12-27 WeylChem Performance Products GmbH Zusammensetzungen mit protonierten triazacyclischen verbindungen und mangan(ii)acetat, verfahren zu ihrer herstellung und bleich- und reinigungsmittel damit

Also Published As

Publication number Publication date
ES8700686A1 (es) 1986-10-16
JPS61111400A (ja) 1986-05-29
DE3566814D1 (en) 1989-01-19
ES546589A0 (es) 1986-10-16
EP0174132A3 (en) 1986-06-11
JPH06212192A (ja) 1994-08-02
CA1257454A (en) 1989-07-18
GB8422158D0 (en) 1984-10-03
US4681695A (en) 1987-07-21
ATE39266T1 (de) 1988-12-15
EP0174132B1 (de) 1988-12-14

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